ChemInform Abstract: Synthesis and Reactions of the Cationic Thiocarbyne (HC(pz)3)(CO)2WC-SMe+. Reactions of the Thiocarbene (HC(pz)3)(CO)2W(η2-CHSMe)2+ with Nucleophiles.
Abstract
The nucleophilic S atom of the CS ligand in (III) is methylated to give the thiocarbyne title complex (V).
ChemInform Abstract
The nucleophilic S atom of the CS ligand in (III) is methylated to give the thiocarbyne title complex (V). Normally, terminal carbyne ligands undergo attack by phosphines at the carbyne carbon, however, in an electron-rich complex such as (V), PMe3 causes carbonylation of the carbyne to yield the η2-ketenyl compound (VII). (IX), prepared by protonation of the carbyne carbon in (V), reacts with nucleophiles to give the carbene adducts (X), (XII) and (XIV). The studies show that the reactivity of the cationic complex (V) is similar to that of the electron-rich neutral carbynes like (HB(Pyz)3)(CO)2W≡C-S-Me (Pyz: pyrazolyl) rather than to the reactivity of Fischer carbynes.
